Sharif Digital Repository

Thermodynamic quantities such as proton affinity (PA) and molecular basicity (GB) for (CaO)n nanoclusters with n=2–16 have been calculated using three computational models of the DFT (B3LYP, M06, PW91, CAM–B3LYP and ωB97XD functionals), MP2, and HF with the cc-PVNZ (n = D and T) basis set in the gas phase. Absolute deviation error (AAD%) indicates that obtained PA and GB values using DFT model and the B3LYP method with mean percentage errors of 0.77 and 0.90 %, respectively, have the higher accuracy than the other methods and models. Owing to the unique physical and chemical properties of ILs, can be used as catalysts, promoters and modifiers of catalyst in many organic reactions. Therefore,... 

In a single chemical plant, the operation of each unit operation is not independent of each other. In the other hand, the main operations are performed in reactors following by several separation steps including distillation and purification units. The total energy requirements are sullied by the heat exchanger networks. The performance of these systems is improved by integration and intensification of the reactor and distillation column in a single unit. The main objective of the present work is to provide an effective design approach to intensify the reactor and distillation column. In a reactive distillation column, the reaction and separation is done in a single unit. Increasing... 

The current thesis deals with designing of functionalized nanoporous catalysts modified with organic groups and ionic liquids and their applications for some challenging organic reactions such as synthesis of adipic acid and fatty acid esterifications. In this condition the catalysts show enhanced activity since the hydrophobicity of the surface can tune by applying organic groups. In this regard, oxidation of cyclohexene was performed using hydrogen peroxide as oxidant in the present of tungstate based task–specific ionic liquids and silica–functionalized ammonium tungstate as green catalysts. The results indicate that adipic acid achieves in high yield with excellent selectivity.... 

In the current work, jatropha oil was studied in the hetrogenious solid catalytic transesterfication reaction. For this perpous, KOH/CNT catalyst which was prepared by dry impregnation method was used. SEM, XRD and TGA were applied for the catalyst characterization. The results showed that for the KOH/CNT catalyst, by increasing the loading of KOH, the activity of the catalyst increased and the most active catalyst was prepared by 20% loading of KOH. The optimum conditions for transesterfication reaction in the percense of this catalyst were: 4.7% catalyst weigth and the 24.5 molar ratio of methanol to oil and also the reaction time of 2 houres which the rate of reaction at this time is... 

This project evaluates the feasibility of using waste salmon fish bones as the reusable and low cost solid catalyst support for synthesis of biodiesel from waste sunflower oil via transestrification method. Calcinated waste fish bone derived hydroxyapatite (HAP) was employed as the supporter for KOH & K2CO3 to prepare an efficient solid base catalyst for biodiesel production. The catalyst were characterized by SEM-EDS, XRD, FTIR, BET, TGA, ICP. The effects of catalyst preparation conditions (such as fish bone and KOH or K2CO3 calcination temperature, loading of KOH or K2CO3 on the support), reaction conditions (such as reaction time, methanol/oil molar ratio, reaction temperature and... 

The purpose of this study is to study heterogeneous nanocatalysts for the production of biofuels by the method of exchange of styrene using oil and methanol as a fossil fuel alternative. Preparation of nanocatalysts, performing characteristic tests and investigating the reaction in different operating conditions in the batch reactor has already been studied. Therefore, in this study, the production of biodiesel fuel using the trans-esterification of canola oil with nanocatalysts in the micro-reactor reactor will be discussed. Previously, a heterogeneous catalyst (lithium based on calcium-lanthanum) was constructed using a co-incineration method and a wet inoculum, and as active and stable... 

The aim of this project is to investigate and synthesize CaO-based nanocatalysts derived from chicken eggshell calcination with alkali metals and sodium-potassium compounds promoters used in the transesterification reaction of canola oil and methanol. Sections of this thesis include the synthesis of nanocatalysts, catalyst characterization tests, and investigation of reaction under optimal conditions. Two groups of catalysts containing different weight percentages of alkali metals based on CaO and 1 %wt sodium-potassium based on CaO with different weight percentages of these two elements were synthesized by wet impregnation method and used in the reaction under optimum condition. Catalyst... 

The aim of this study is developing and investigating heterogeneous catalysts based on natural calcite for the transesterification of canola oil and methanol in order to produce biodiesel as a renewable and alternative fuel for fossil fuels. At first calcite was calcined at high temperature to decompose calcium carbonate to calcium oxide. Afterward, Mg-Zr/CaO catalysts were prepared with mass ratio of 2:1 Mg:Zr and different weight percent(2.5, 5,7.5 and 10 wt%) on calcite supported by impregnation method. In order to characterized synthesized catalysts used different analysis such as energy dispersive X-ray (EDX) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy... 

This study aims at synthesizing and investigating of heterogeneous catalysts for biodiesel production as an alternative to fossil fuel with a transesterification reaction of sunflower oil and methanol. Three main sections of this thesis concern the synthesis of clay base catalyst, characterization analysis, and investigation of the transesterification reaction under different conditions. Talc clay base catalyst impregnated with a 40 wt.% of K2CO3 as active and stable catalysts to study the transesterification reaction of sunflower oil and methanol for biodiesel production. Synthesized catalysts have been characterized by power X-ray diffraction (XRD), scanning electron microscopy (SEM),... 

Nowadays, due to depletion of fossil fuels and the emission of green house gases, biodiesel has attracted lots of attention as a renewable, non-toxic, and biodegradable fuel. Biodiesel can be produced from different resources such as vegetable oil, animal fat and algae oil. In this study, waste frying oil was used as a raw material that can reduce the probable hazardous effects of its disposal and produce a clean fuel at the same. Biofuel was produced through an enzymatic method using the whole cell of Rizopu oryzae (a filamentous fungus) in both immobilized and free forms. In order to find the optimum conditions for biodiesel production, four variables including temperature, methanol to oil... 

The aim of this project is to fabricate and study heterogeneous CaO-based nanocatalysts with lithium and zinc enhancers for the esterification reaction of rapeseed oil and methanol to produce biodiesel as a renewable and alternative fuel for fossil fuels. Is. First, Zn-Li / CaO catalysts with weight ratio Li: Zn: CaO, 2: 2: 7 and by combining different percentages of Li100% promoter, Li75% -Zn25%, Li50% -Zn50%, Li25% -Zn75%, 100% Zn were made on the basis of CaO by wet inoculation. Characterization tests to evaluate the structure and characterization such as X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (EDX) spectroscopy, Bruner-Emmett-Teller... 

Clean and Renewable energies are one of the most important part of global policy. In order to reduce greenhouse gas emissions mostly from fossil fuels, many countries have introduced biofuels to avoid depletion of fossil fuels and decrease the pollution. In Iran, large dependency on crude oil and natural gas resources cause barriers for utilization of biofuels. The country has plenty of biomass resources that may guide national decision makers toward biofuels.In this study, biomass supply chain to produce biofuel is studied to reach sustainability. The model enables us to depict the optimal path to reach the economic, environmental, and social sustainability through the whole supply chain.... 

The current study deals with application of a surfactant-like Brønsted acidic ionic liquid (IL) 1-dodecyl-3-methylimidazolium hydrogensulfate (catalys 1) for Mannich reaction at room temperature. The reaction has been efficiently proceeds in water as solvent without using any harmful and expensive organic additives. Our observation has been shown that the reaction is selective for cyclohexanone and no product was observed by using cyclopentanone at room temperature. Density functional theory (DFT) calculations were performed to provide evidence about the nature of reactivity of the cyclohexanone/cyclopentanone. The activity of the catalyst 2 (1-dodecyl-2,3-dimethylimidazolium... 

The aim of this project is to inventigate and synthesize CaO-based nanocatalysts with metal promoters of magnesium and lithium by wet impregnation and coprecipitation methods, which are used in the transesterification reaction of canola oil and methanol. Sections of thesis include review of before researches , synthesis of nanocatalysts, catalyst characterization tests,and investigation of reaction under optimal conditions. In wet impregnation method, nanocatalysts were made with 5% by weight of lithium-magnesium on the basis of CaO and with different weight percentages of these two elements. In the co-precipitation method , catalysts with a combined base of calcium oxide/magnesium oxide ... 

Reduction in the oil reserves level and the increasing of fossil fuel prices and GHG has led to growing value of attention to biodiesel. Reserves of fossil fuels are running out and should have proper alternative for them. Environmental benign and renewable properties of biodiesel make it consider suitable candidate to replace fossil fuels.
In this study, continuous production of biodiesel and optimization of important and influential parameters have been investigated. The method is concluded of trans esterification of soya oil with methanol as feed in presence of homogeneous catalyst of NaOH. The reactor was simple with high efficiency and low operational and investment cost. The... 

In this work the transesterification reaction of waste cooking oil in the present of solid catalyst as a type of solid-liquid catalytic reaction, has been studied. For this purpose, two types of alkali solid catalysts were synthesized. CaO-ZrO2 and KOH/γ-Al2O3 catalysts were prepared by co-precipitation and impregnation method, respectively. These catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF), BET surface area, and temperature programmed desorption of CO2 (TPD-CO2). The obtained results for the CaO-ZrO2 catalysts indicate that with increasing Ca/Zr atomic ratio, the activity of catalysts increases, but the stability... 

Superparamagnetic core/shell nonporous (S1) and core/shell/shell mesoporous (S2 and S3) nanocomposite magnetite/silica particles with a magnetite cluster core of 130±30 nm, a nonporous silica shell of 90±10 nm thickness, and a mesoporous silica shell of 70±15 nm thickness were prepared thorough a simple method. Mesoporous particles were prepared with two BJH pore sizes (2.44 for S2 and 3.76 nm for S3 particles, respectively). The fabricated S1, S2 and S3 particles present high saturation magnetization values of 20, 13 and 17 emu/g, respectively. As a biological application, the lipase from Pseudomonas cepacia was successfully immobilized onto the amino-functionalized nanocomposite particles... 

Increasing emissions of greenhouse gases from one hand and decline in the fossile resources of energy on the other hand has raised the motivation of searching for renewable sources. Biodiesel, because of having perfect feature for replacing with petroleum diesel, has been considered as candidate for this purpose. Using enzymatic reaction is one of the methods for biodiesel production. Understanding the kinetics of this reaction is important to achieve higher production rates.
In present work, the kinetic of transesterification of castor oil with use of Novozyme 435 (as enzyme) was investigated. Enzymatic biodiesel production is a bi-substrate (oil and alcohol) reaction. Genetic algorithm... 

Biodiesel has drawn the attention of many researches to itself as a replacing source for crude oil, recently. Transesterification is one of the most popular methods used for biodiesel production. Enzyme transesterification is a more simple method in comparison with acidic or basic transesterification. However, the high price and low yield of enzyme transesterification has caused many obstacles in its application. Enzyme engineering has gained much attention as a way to improve enzyme performance. In this thesis, biodiesel production by a native enzyme named Bacillus thermocatenulatus, and two engineered-enzymes is studied. First, effective parameters and variables in biodiesel production by...